Photographic developer



Patented Dec. 15, 1942 PHOTOGRAPHIC DEVELOPER- Wlllard D. Peterson, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application August 8, 1941, Serial No. 406,025

'7 Claims.

This invention relates to photographic developers and more particularly to photographic developers in which a solubilizing group is attached to the aromatic ring system of the developer through an ether linkage. V

It is known that photographic developers of the p-phenylene diamine type are valuable compounds for producing fine grain black and white photographic images and also that these compounds, especially when they contain alkyl substituents, are useful as developers in the process for producing colored photographic images. The p-phenylenediamine developers, however, have several defects. One disadvantage of these developers is that they are'not highly soluble in the developing solutions. Another disadvantage is that they are highly allergenic, that is, they are poisonous to the human skin and are, therefore, somewhat dangerous to use. When the p-phenylenediamines are used in the color development process, it has also been found that they do not always produce the desired color in the final image.

It is therefore, the principal object of my pres-- ent invention to provide a new class of photographic developing agents of the p-phenylenediamine type. A further object is to provide photographic developing agents which are more soluble in the developing solutions than compounds previously used. A still further object is to provide developing agents which are less allergenic, that is, less poisonousto the human skin than compounds hitherto known. A still further object is to provide photographic developing agents of the substituted p-phenylenediamine type which are useful in photographic color processes for the purpose of producing images of the desired color.

These objects are accomplished by the present invention by the use as developing agents 'of compounds having the following general formula:

wherein R1 and R2 are alkyl radicals, heterocyclic substituted alkyl radicals such as tetrahydrofurfuryl, or' aryl substituted alkyl radicals such as benzyl, or R1 and R2 together represent the atoms necessary to conetmplate a hetero-- cyclic system, and R3 represents an alkylene radical having attached thereto a water solubilizing group such as hydroxyl, carboxyl, sulfonic acid, amino or acid amide.

Specific compounds which I contemplate using are as follows:

CHa-C H1 CH; 011,- H H;

l 0 C H10 H10 H r NH; 3-(fl-hydroxy-othoxy)-i-amlno-N-ethyl-N-tetrahydroiurfuryl aniline (2) oomomomon CzHs /N NH: C2 5 3-( -hydroxy propoxy)-4-aminodlethylanlline a oomomon CaHs /N NH,

3-(flhydroxy-ethoxy)+aminodiethylaniline (4) OCHlCHlO CHzCHaOH OH:

NH; C I 3-(wl1ydroxy diethylene glyool)-4-amino di-methylanillne (5 OCHr-CH- CHIOH H c NH: Glycerol-a-2amiuo-5-propyl-benzylamino phenyl) other 01H; CIHU 0CH1-CH-CH:-0

(in NH: NH: l,3 di(?-amino-5-dlethylamino phonoxy) propanol-2 Z-amino-B-diethylamino-phenoxy N-(o-carboxy phenyl) acetemide OCHSCHISOQH 2'amino-5-N-ethyl-N-benzylamino-B-phenoxy ethyl sullonate Compound (2) was prepared by reducing the p-nitroso derivative of 3-(y-hydroxy propoxy)- diethylaniline in weak hydrochloric acid solution with slightly more than the theoretical quantity of zinc dust. This reaction mixture was made alkaline, extracted with ether, the ether extract washed with water and concentrated. The final product was distilled under two millimeters pressure at 184-188 C. Nitrogen analysis showed the product to be pure.

Compound 3 was prepared by a similar procedure starting with 3-( s-hydroxyethoxy) diethylaniline. It boiled at 156-160 C. at two millimeters pressure.

These compounds may be further substituted in the aromatic ring with other groups including halide, amino, substituted amino, azo, alkyl and aryl groups. These groups have a tendency to alter the color of the final dye image and the color of the image may be controlled in this way.

When used for the formation of colored photographic images, the developers of my invention may be used in conjunction with any well knowncoupler compounds such as those described in Fischer U. S. Patent- 1,102,028, June 30, 1914; Mannes and Godowsky U. S. Patent 2,108,602, February15, 1938; Mannes, Godowsky and Peterson U. S. Patent 2,115,394, April 26, 1938; and 4 Mannes, Godowsky and Peterson U. S. Patent 2,125,337, August 9, 1938.

'The following examples, which are illustrative only, indicated developingsolutions which may be used according to my invention.

Example 1 A. 3-( -hydroxyl propoxy)-4-amino diethylaniline grams 2 Sodium sulphitedo Sodium carbonate do 30 Water in .1000

13. p-naphthoyl aeetonltrile. ...-gram.. 1 Acetone 50 Add a to A.

J Example 2 The coupler used to form a colored image may be incorporated in the emulsion-layer prior to exposure and a colored image formed by development in the following solution:

2-(p-hydroxy propoxy) -4-aminodiethylaniline grams 2 Sodium sulphite do 0.5 Sodium car do 30 Water to M 1000 Example 3 For the formation of a fine-grain black and white image, the following developing solution may be used: 4 -3-(p-hydroxy-ethoxy) 4 aminodiethylaniline grams 5 Sodium nlphite dn Sodium carbon do Water to 1000 These compounds are more active as color developers than the unsubstituted p-aminodialkylaniline and are more soluble in water. They are also less toxic than the unsubstituted p-amin'odialkylanilines.

The developing agents described in the present application may be used to form photographic images by development of exposed silver halide contained in the usual gelatin carrier or in carriers such as collodion, water permeable cellulose esters, or water permeable synthetic resins. The sensitive layers may be carried on any suitable support such as glass, paper, cellulose esters I or synthetic resins. They may be used with multi-layer films where two or more layers are coated on the same side of a support or where the layers are coated on the opposite sides of a support.

I claim:

1. A photographic developing agent having the following general formula:

wherein R1 and R2 are substituents selected from the group consisting of alkyl, heterocyclic substituted alkyl, aryl substituted alkyl, and the atoms necessary to complete a heterocyclic system; Ra=an alkylene radical having attached thereto a hydroxyl solubilizing group.

2. A photographic developing agent comprising 3- (y-hydroxypropoxy) -4 -aminodiethylaniline.

3. A photographic developing agent comprising 3- (p-hydroxyethoxy) -4-aminodiethylaniline.

4. A photographic developing solution for producing a colored image comprising 3-( -hydroxypropoxy) -4-aminodiethylaniline as the developing agent, and a compound which couples with the developing agent on photographic development to form a colored image. I

5. A photographic developing solution for producing a colored image comprising Z-(p-hydroxyethoxy). -4-aminodiethylaniline.

6. The method of producing a colored photophic image in a gelatino silver halide emulsion layer which comprises developing said emulsion with a developing agent having the following general formula:

ence oi. azcompound which couples with the developing agent on development.

7. The method of producing a colored photographic image in a gelatino silver halide emulsion layer which comprises developing said emul sion with a. developing agent having the following general formula:

R1 wherein R1 and R2 are substituents selected from 7 10 the group consisting of alkyl, heterocyclic substituted alkyl, aryl substituted alkyl, and the atoms necessary to complete a heterocyclic system; Ra=an alkylene radical having attached thereto a water solubilizing group; in the .presence of a phenolic coupler compound.

WILLARD D. PETERSON. 

